Chiral α-arylalkanoic acids and derivatives are core structures in many drug molecules. For example, the profen family of nonsteroidal anti-inflammatory drugs are all α-arylpropionic acids, including blockbusters such as Ibuprofen, Naproxen, and Ketoprofen. The enantiomers of these compounds are known to display substantially different pharmacological profiles and Naproxen is sold in its optically pure (S)-form. To achieve convergent and efficient synthesis, aryl groups are best introduced with concomitant establishment of chirality. However, asymmetric α-arylation of esters using either aryl-metal reagents or aryl electrophiles has met only with limited success. One example was recently reported by Fu et al., in which arylsilanes were used as equivalent of “aryl-metal” reagents. These compounds underwent Ni-catalyzed coupling with racemic α-bromoester to give products containing tertiary centers in high enantiomeric excess (ee). A more straightforward disconnection involves C—C bond formation between aryl halides/sulfonates and enolate anions. Successful examples of this kind with excellent ee are surprisingly scarce. In the work by Buchwald and coworkers, aryl chlorides were used to couple with enolates generated in situ from γ-butyrolactone and a strong base. Although a high level of ee was achieved, the method was limited to the formation of quaternary stereocenters. In fact, all of metal-catalyzed, enantioselective arylations of carbonyl compounds (including ketones, aldehydes, oxindoles and α-methylacetoacetates) suffered from the same limitation. The challenge in producing alpha asymmetric tertiary centers lies in the increased acidity of the α-hydrogen of the monoarylation product than the starting material and therefore, these products can be readily deprotonated under basic conditions. The deprotonation can eventually lead to racemization and in some cases, double arylation. Thus, there remains a need in the art for new and improved methods and reagents for the efficient α-arylation of ester anions to produce tertiary centers with high ee.